CN103261325B - For the lining of air accumulator - Google Patents

For the lining of air accumulator Download PDF

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Publication number
CN103261325B
CN103261325B CN201180059418.4A CN201180059418A CN103261325B CN 103261325 B CN103261325 B CN 103261325B CN 201180059418 A CN201180059418 A CN 201180059418A CN 103261325 B CN103261325 B CN 103261325B
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Prior art keywords
lining
polyamide
nucleator
total amount
respect
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CN103261325A (en
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科纳德·杜勒特
凯塔琳娜·托米奇
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DSM IP Assets BV
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DSM IP Assets BV
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D22/00—Producing hollow articles
    • B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/03—Thermal insulations
    • F17C2203/0304—Thermal insulations by solid means
    • F17C2203/0308—Radiation shield
    • F17C2203/032—Multi-sheet layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/03—Thermal insulations
    • F17C2203/0391—Thermal insulations by vacuum
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0604—Liners
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/066—Plastics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0663—Synthetics in form of fibers or filaments
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0675—Synthetics with details of composition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2209/00—Vessel construction, in particular methods of manufacturing
    • F17C2209/21—Shaping processes
    • F17C2209/2109—Moulding
    • F17C2209/2127—Moulding by blowing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/011—Oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/012—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/014—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/016—Noble gases (Ar, Kr, Xe)
    • F17C2221/017—Helium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/03—Mixtures
    • F17C2221/032—Hydrocarbons
    • F17C2221/033—Methane, e.g. natural gas, CNG, LNG, GNL, GNC, PLNG
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/03—Mixtures
    • F17C2221/032—Hydrocarbons
    • F17C2221/035—Propane butane, e.g. LPG, GPL
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/03—Dealing with losses
    • F17C2260/035—Dealing with losses of fluid
    • F17C2260/036—Avoiding leaks
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0142—Applications for fluid transport or storage placed underground
    • F17C2270/0144—Type of cavity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The present invention relates to a kind of lining that comprises polymer composition for air accumulator, it comprises: i. polyamide A; With the total amount of ii. with respect to described polymer composition, content is the nucleator of at least 0.001 % by weight; With the total amount of iii. with respect to described polymer composition, content is the impact modifying agent of at least 1 % by weight. The invention still further relates to a kind of air accumulator that comprises the structural fibrous composite that contains continuous carbon fiber or glass fibre, and a kind of method of manufacturing lining by blow molding.

Description

For the lining of air accumulator
The present invention relates to a kind of lining that comprises polymer composition for air accumulator, and relate to bagContaining the air accumulator of this lining.
Prior art
Air accumulator is known, for example, be called as composite packaging pressure vessel (compositeOr vacuum heat-insulation can container overwrappedpressurevessel). That air accumulator comprises is thin, conventionallyWith the unstructuredness lining of structural fibrous composite parcel, this lining is sent out meter and is used under pressureContaining fluid or gas. This lining is used for providing barrier between fluid or gas and composite, withThe chemical degradation of Leakage prevention and structural fibrous composite. In the ordinary course of things, apply containment vesselFor preventing the protecting screen of impact failure. The most frequently used composite is fibre-reinforced polymer. RightIn lining, the most frequently used is polyethylene, described in US2002088806. Close with sizeStress metal tank compare, the advantage of the tank of these types is that its weight is lower. But, this liningIn shortcoming be that the gas oozing out from lining may make fiber become fragile. In US20090203845, describeA kind of lining with improved barrier property, it comprises polyamide, copolyamide and anti-impactHit material. The shortcoming of this lining is that barrier is still not enough.
Target of the present invention
Target of the present invention is to provide a kind of for air accumulator and show the lining of improved barrier propertyIn.
Detailed Description Of The Invention
Already surprisingly found, a kind of lining that comprises polymer composition for air accumulator demonstratesImproved barrier property, described lining comprises:
I. polyamide A; With
Ii. with respect to the total amount of polymer composition, content is the nucleation of at least 0.001 % by weightAgent; With
Iii. with respect to the total amount of polymer composition, content is the impact modified of at least 1 % by weightAgent.
Lining according to the present invention has improved barrier property. This lining makes fiber degradation less, andCompared with air accumulator known in the state of the art, in air accumulator, allow thinner lining or layer still less,This will save material and simplify technique. Another one advantage is to use according to lining of the present invention sightExamine bending (buckling) still less. For example, in the time that the pressure in tank is low when tank opening (), byThe gas expansion that has infiltration and exist between lining and other layers, now bends.
Another advantage of lining of the present invention is, the optional vacuum space existing (for super heat insulation andExist) the also protected gas permeation that avoids better.
Term " gas " is interpreted as and comprises various gas at this, but it may in storageComprise liquid part. The example of gas comprises biogas and natural gas. Concrete example comprise hydrogen,Methane, butane, propane, helium, nitrogen and oxygen.
Lining may reside in the inner side of tank, thereby contacts with the liquid that will store and/or gas. Exist, lining also may reside in the outside of tank when the vacuum space, thereby is positioned at the outside of vacuum space and tankBetween. Tank also can comprise the combination of lining, and for example, one in inner side, and one in outside.
According to another advantage of lining of the present invention be, it has good barrier property, simultaneously toolThere is enough rigidity. Surprisingly, have found that during the manufacture of lining the depositing of nucleatorAffecting hardly blow molding performance.
Polyamide A
Polyamide A in the lining that contains polymer composition can be any hemicrystalline polyamide orIts mixture and copolyamide.
" hemicrystalline polyamide " is understood to include the polyamides with crystal region and amorphous area in this articleAmine. Suitable polyamide comprise fatty polyamide as PA6, PA66, PA46, PA410,PA610, PA11, PA12, PA412 and composition thereof, also comprise semiaromatic polyamide composition. SuitableSemiaromatic polyamide composition comprise the polyamide based on terephthalic acid (TPA), for example PA6T, PA9T,PA4T, PA6T6I, PA10T and PAMXD6, PAMXDT and copolyamide thereof andIts mixture, also comprises the mixture of aliphatic and semiaromatic polyamide composition.
Preferably, polyamide A is selected from the group of PA6, PA66 and composition thereof, because do like thisAdvantage is that these polyamide are all easy to obtain, and have good level of interpenetration, Yi JiliangGood extension level or impulse withstand level.
Nucleator
Lining according to the present invention is with total amount at least 0.001 % by weight with respect to polymer compositionAmount comprises nucleator.
Term " nucleator " is well known by persons skilled in the art, refers to such material, this thingMatter is formed for the core of crystal growth in polymer melt in the time being impregnated in polymer. Nucleator comprises exampleAs thering is the polyamide of higher melt temperature than the melt temperature of polyamide A. Higher melting temperatureDegree is understood in this article, preferably than the melting temperature of at least 10 DEG C of the melt temperature height of polyamide ADegree, more preferably than the melt temperature of at least 20 DEG C of the melt temperature height of polyamide A, most preferably than poly-The melt temperature of at least 50 DEG C of the melt temperature height of acid amides A.
The polyamide that is suitable as nucleator comprises all polyamide of mentioning above, but additional conditionsFor melt temperature is higher than the melt temperature of polyamide A. Preferably, PA46, PA4T or PA410 quiltAs nucleator.
Preferably, with respect to the total amount of described polymer composition, nucleator is with 0.01wt%'s at leastAmount exists, and more preferably exists with the amount of 0.02wt% at least, most preferably deposits with the amount of 0.05wt% at least.
Other nucleators comprise micro-talcum (microtalcum), carbon black, silica, titanium dioxideAnd nanoclay.
Preferably, with respect to the total amount of described polymer composition, nucleator is with the amount of 5wt% at the mostExist, more preferably exist with the amount of 4wt% at the most, most preferably exist with the amount of 0.15wt% at the most.
Preferably, nucleator is micro-talcum. This micro-talcum preferably has that to be less than the intermediate value of 1 micron straightFootpath, is more preferably less than the median diameter of 0.7 micron, and the intermediate value that is even more preferably less than 0.6 micron is straightFootpath.
The benefit of doing is like this, compared with the talc particle higher with median diameter, this micro-talcum can be moreEffectively improve barrier property.
Micro-talcum can be present in polymer composition with low-down amount, for example, with respect to describedThe total amount of polymer composition is the amount of 0.001wt% at least, and the preferred at least amount of 0.01wt% is more excellentSelect at least amount of 0.02wt%, even more preferably the amount of 0.04wt% at least. Preferably, with respect to instituteState the total amount of polymer composition, micro-talcum can be present in polymer group with the amount of 0.8wt% at the mostIn compound, the more preferably amount of 0.5wt% at the most, the even more preferably amount of 0.2wt% at the most.
According to the advantage of the amount of micro-talcum of the present invention be, at-30 DEG C to keeping enough low-temperature impactsProperty.
In one embodiment, PA6 is selected as polyamide A, simultaneously nucleator be selected from PA66,In the group of PA46, PA410 and PA4T.
In one embodiment, PA66 is selected as polyamide A, simultaneously nucleator be selected from PA46 andIn the group of PA4T.
Impact modifying agent
With respect to the total amount of polymer composition, lining according to the present invention is with the amount bag of 1wt% at leastContaining impact modifying agent. Impact modifying agent itself is known, its for not only comprise non-polar monomer (asAlkene) and comprise polarity or reactive monomer (for example acrylate and contain epoxy, acid or acid anhydridesMonomer) rubber-like polymer. Example comprises ethene and (methyl) acrylic acid copolymer or acid anhydridesGroup functionalization's ethylene/propene copolymer. The advantage of impact modifying agent be they not instrument improve polymerThe impact strength of composition, also contributes to the increase of viscosity.
Preferably, the amount of impact modifying agent is 5wt% at least, more preferably 7wt% at least, even morePreferably 10wt% at least. The benefit of doing is like this that impact strength is good.
Preferably, with respect to the total amount of polymer composition, the amount of impact modifying agent is at the most 60Wt%, more preferably 50wt% at the most, even more preferably 30wt% at the most. Most advantageously impact and changeThe amount of property agent is 7-20wt%. The benefit of doing is like this to keep enough barrier properties to have concurrently well simultaneouslyRigidity property. Preferably, impact modifying agent is core-shell type impact modifying agent. Show core-shellType impact modifying agent is less on the impact of barrier property.
Other additives
Can optionally comprise other additive according to lining of the present invention, as filler, colouring agent,Branching agent, releasing agent and lubricant.
Suitable filler is inorganic filler, as clay, mica, talcum, glass marble. Fortifying fibre isFor example glass fibre or carbon fiber. With respect to the total amount of polymer composition, daiamid composition is preferredThe glass fibre that ground comprises 1-60wt%, as fortifying fibre, more preferably comprises the glass of 10-45wt%Fiber, as fortifying fibre, most preferably comprises the glass fibre of 10-20wt% as fortifying fibre. OneAs, the diameter of suitable glass fibre is 5-20 micron, preferably 8-15 micron, and for being suitable forIn the coating of polyamide. The advantage of the polymer composition that contains glass fibre is, the intensity of its increaseAnd rigidity, particularly also like this under higher temperature, thus allow approaching in polymer compositionAt the temperature of the fusing point of polymer, use. With respect to the total amount of polymer composition, carbon fiber can be withThe amount of 30wt% exists at the most.
The manufacture of lining
Can manufacture lining by blow molding or injection moulding. Injection mo(u)lding is preferably with bivalve mouldingForm carry out, afterwards shell is welded into lining. While manufacture by blow molding, lining also preferably wrapsContain branching agent to allow the higher viscosity of polymer composition.
Blow molding is understood to include at least the following step in this article:
A. heated polymerizable compositions is to obtain uniform viscous liquid;
B. form parison (parison) by described viscous liquid;
C. make parison swell and make it near mold cavity by gas-pressurized, until it is cooling and solidChange and form parts;
D. open described mould;
E. penetrate these parts.
Preferred method for the manufacture of lining is blow molding, because this can obtain larger lining,And avoid using extra welding procedure step.
Air accumulator
The invention still further relates to and a kind ofly comprise structural fibrous composite and according to the storage of lining of the present inventionGas tank. Structural fibrous composite generally includes continuous carbon fiber or glass fibre.
Embodiment
Material therefor:
Comparative example A and B:HDPE
The PA6 that embodiment 1:89.67wt% relative viscosity is 2.5,
0.5wt% branching agent,
9.75wt% impact modifying agent (ethylene copolymer of maleic anhydride (MAH) grafting),
The micro-talcum of 0.08wt%, as nucleator.
The PA6 that embodiment 2:79.82wt% relative viscosity is 2.2,
20wt% impact modifying agent (ethylene copolymer of maleic anhydride (MAH) grafting),
The micro-talcum of 0.08wt%, as nucleator.
Micro-talcum
Median diameter is 0.50 micron, 99% be less than 5 microns, 92% be less than 2 microns, and75% be less than 1 micron.
Measure the method for testing of helium permeability
Method of testing comprises the stable state transmitance of evaluating gas permeation plastics (film, sheet material). InstallThereby sample forms barrier between two chambers of gas permeation unit. A chamber is included in appointmentHigh pressure under test gas, in another chamber, collect the gas of infiltration, and bring this gas into inspectionSurvey device. The surface of known sample, can calculate gas permeation rate (gastransmissionrate),, under test condition, in the unit interval, pass through the quantity of the given gas of plastic sheeting per surface.
The test of helium permeability is to carry out at the temperature of 40 DEG C and 25 DEG C, be all 0% relativelyUnder humidity. The thickness of all test samples is 0.4 millimeter, and helium dividing potential drop is 6Bar. Calculate heliumPermeability (Heliumpermeability), the ratio of gas permeation rate and helium dividing potential drop is multiplied by filmThickness. The unit that represents permeability is cm3mm/m2dayatm。
Table 1: the result of helium permeability rate
* definite composition refers to " material therefor " as above; N.m. be undetermined.
Result in table 1 clearly illustrates that, compared with HDPE, adopts according to lining of the present inventionPolymer composition demonstrate the permeability of reduction.
Also at 40 DEG C, measured the permeability of nitrogen by the same program for helium. Further logicalThe method described in ISO15105-1 crossed is measured the permeability of methane at 40 DEG C. For according to thisThe polymer composition that the lining of invention adopts, nitrogen and the methane permeability at 40 DEG C is equalBe less than 1cm3mm/m2Dayatm. And for HDPE as a comparison, the permeability of nitrogenFor 124cm3mm/m2Dayatm, the permeability of methane is 341cm3mm/m2Dayatm. TheseResult also shows, compared with HDPE lining, lining according to the present invention has excellent barrierEnergy.
Use capillary rheometer (Rheograph6000) measure melt strength. TestingCheng Zhong, uses constant output, the line of extruding polymerization compositions, (data: baking box diameter12mm, Vpiston=0.1mm/sec, capillary 40/2, capillary pipe length is 40mm, TMelting=240 DEG C). During melt strength is measured, with constant acceleration (1.2mm/sec2) elongation instituteState wire rod. Measure different stretch than under melt strength (cN).
Find surprisingly, this value of lining according to the present invention polymer composition used is for approximately15cN, it is with the polymer composition containing nucleator is unsuitable.

Claims (11)

1. one kind by the combination of polymers that comprises for air accumulator of blow molding or injection moulding manufactureThe lining of thing, it comprises:
I. polyamide A; With
Ii. with respect to the total amount of described polymer composition, content is at least 0.01 % by weight and at the most 4The nucleator of % by weight, wherein said nucleator is selected to be had higher than polyamide AThe polyamide of melt temperature and the group of micro-talcum; With
Iii. with respect to the total amount of described polymer composition, content is the impact modified of at least 1 % by weightAgent.
2. lining as claimed in claim 1, wherein, has higher melting temperature than polyamide AThe described polyamide of degree is selected from the group of PA46, PA410, PA4T.
3. lining as claimed in claim 1, wherein, described polyamide A is PA6, and described inNucleator is selected from the group of PA66, PA46, PA410, PA4T.
4. lining as claimed in claim 1, wherein, described polyamide A is PA66, and instituteState the group that nucleator is selected from PA46 and PA4T.
5. lining as claimed in claim 1, wherein, described nucleator is micro-talcum.
6. the lining as described in any one in claim 1-5, wherein, with respect to described polymerThe total amount of composition, described nucleator exists with the amount of 0.05wt% at least.
7. the lining as described in any one in claim 1-5, wherein, with respect to described polymerThe total amount of composition, described nucleator exists with the amount of 0.05-0.15wt%.
8. the lining as described in any one in claim 1-5, wherein, with respect to described polymerThe total amount of composition, the content of described impact modifying agent is 7-20wt%.
9. the lining as described in any one in claim 1-5, wherein, described impact modifying agent isCore-shell type impact modifying agent.
10. air accumulator, it comprises the lining as described in any one claim above and contains continuouslyCarbon fiber or the structural fibrous composite of glass fibre.
11. 1 kinds of methods for the preparation of the lining as described in any one claim above, at leastComprise the following steps:
A. heat described polymer composition to obtain uniform viscous liquid;
B. form parison by described viscous liquid;
C. make described parison swell and make it near mold cavity by gas-pressurized, until it is coolingAnd solidify to form parts;
D. open described mould;
E. penetrate described parts.
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